Light sensitive diazotype material



Patented Oct. 13, 1942 I Rochester, N. E,

Company, Rochester, N. Y.,

New Jersey ..Arnold Weissberger and Waldemar Vanselow, assignors toEastman Kodak a corporation of No Drawing. Application October 15, 1940,Serial No. 361,263

6 Claims.

This invention relates to the preparation of wherein R represents aphenyl nucleus having the amino group in position para or ortho to N,and

Z represents the non-metallic elements necessary to complete aheterocyclic nucleus selected from the group consisting of a morpholinenucleus, and a piperidine nucleus. In addition to the amino group, R cancontain one or more nuclear monovalent substituents such as an alkylgroup represented by methyl, ethyl, propyl, butyl for example, an alkoxygroup represented by methoxy, ethoxy, propoxy, butoxy for example, ahalogen such as chlorine, bromine, fluorine, iodine, or a sulphonic acidradical.

We have found that the above described diazo derivatives ofN-p-aminophenyl-morpholines and -piperidines are stable compounds underordinary conditions, but are highly sensitive to light, decomposing moreor less completely in proportion to the intensity of the light and theperiod of exposure. Since they are also capable of condensing withcertain aryl compounds, as well as with their own partial decompositionproducts in the presence of alkaline substances to form intenselycolored azo dyes, we have furthere found that these diazo derivativesare valuable as light sensitive components in diazotype copyingmaterials. In the presence of selected coupling components on a suitablesupport, they yield on exposure to light behind a pattern such as a linedrawing, printed matter or similar contrasty subject matter andsubsequent alkaline processing, images having dark lines and tonescontrasted to almost white or slightly gray or tan fields. As will bemore fully apparent from the examples given, we can prepare our newdiazotype materials by a number of methods. For example, the base orsupport carrying or containing the light sensitive compounds can be apaper, a cloth, a film such as prepared from an organic derivative ofcellulose, synthetic resin such as a polyvinyl acetal, regeneratedcellulose, a glass plateor a sheet of metal, the sensitizing materialsbeing applied by coating, dipping, brushing, spraying, dusting or by anyother means known to one skilled in the art. Ordinarily, the sensitizingcompounds are applied from solutions containing them, eitheralternatively with a solution of one or more of the diazo compounds ofour invention and a solution of the selected coupling component, or, thecompounds can be dissolved in a common solvent and applied as above,usually with an acid compound present as a stabilizer. In some cases, itmay be desirable to add a thickening or emulsifying agent to thesolution or solutions such as gelatin, polyvinyl alcohol, gumtragacanth, a higher fatty acid glycerylsulfate, and the like. Thesolution concentrations of the sensitizing compounds can be variedwithin wide limits, the preferred range being up to about 2% by weightof the diazo compound, and about the same concentration of the couplingcompound.

It is an object of the invention, therefore, to provide a lightsensitive diazotype copying material which combines the advantages ofgood keeping qualities, high degree of sensitivity to light, andprovides prints which are characterized by good stability, sharpness andcontrast.

The aminophenyl piperidine compounds may be prepared by reducing thenitro piperidine compounds prepared in general by the method describedin Journal Chemical Society (1927) pages 1113 and 1122. The aminophenylmorpholine compounds may be prepared by condensing the desired anilinecompound with a beta-beta-dihalogen alkyl ether such asbeta-beta'-dichlorodiethyl ether, sym. dichloro-di-isopropyl ether andother similar kind of haloalkyl ethers.

The following examples further illustrate the preparation andapplication of our new light sensitive diazotype copying materials.

-EXAMPLE 1 A diazo solution was prepared by treating 5.43 grams ofN-p-(aminophenyl) -morpholine hydrochloride dissolved in 0. cs. of waterwith a slight excess of nitrous acid. A piece of white paper was dippedin this solution for a short period, the excess of solution removed, thepaper dried and then dipped in a 1% solution of B-naphthol in ethylalcohol. The dried sensitized paper was exposed behind a positive to aquartz mercury vapor arc. After a few minutes, the image was developedin an atmosphere of ammonia maintained at slightly higher than roomtemperature. The positive image obtained at once was dark brown in coloron an almost white field.

In place of N-p-(aminophenyl) -morpholine hydrochloride, there may besubstituted 9 grams of N-p- (amino-m-tolyl) -m o r p h o l i n e sulfatewhich produces a dark brown black image on an almost white field turningtan colored after several months, or, there may be substitutedapproximately 2 grams of N- (4-aminophenyl) morpholine-2-sulfonic acidwhich yields a dark red image on a pale pink field, or, there may bepholine which, with p-naphthol coupler produces a red image on a palepink field, and with resorcinol coupler an orange image on a pale tanfield.

ExAMrLn 2 The diazo solution prepared as in Example 1 was allowed tostand until a suflicient quantity of the diazonium compound hadhydrolyzed to provide a coupler. A piece of white paper was then bathedin the solution, the excess solution removed, and the paper dried. Uponexposure and development, an image was obtained which was dark brown ona tan field turning with time to a black image on a pale gray field.

ExAMru: 3 '7 grams of N-p-(aminophenyl) -piperidine dihydrochlorideCHI-CH,

OKs-CH! were diazotized with nitrous acid in 100 0. cs. oi! I aqueoussolution. A piece of white paper was treated in this solution, dried,and then treated in a 1% alcoholic solution or fl-naphthol and againdried. After exposure and development as in Example 1, a blue blackimage on a white field was obtained.

In place oi. N-p-(aminophenyD-piperidine dihydrochloride, there may besubstituted 7.5 grams oi N-(2-chloro-4-aminophenyl) piperidine sulfatewhich produces a bright red image on an almost white field.

EXAMPLE 4 5 grams of N-p-(amino-m-anisyl) -morpholine were diazotized in100 c. es. of aqueous solution, and a piece of paper treated in thissolution, dried, and then treated with a 1% alcoholic solution of2,4-dichloro-1-naphthol, and the paper again dried. After exposurethrough a positive pattern and development in ammonia vapor, an imagewas obtained which was very dark brown on a pinkish gray field, turningafter five months to a black image on a slightly draker field.

EXAMPLE 5 added to 80 c. cs. of solution containing 0.5 gram of tartaricacid and the diazonium salt of 2.5 grams of N-p- (aminophenyl)-piperidine dihydrochloride. Several pieces of filter paper and ragstock paper were sensitized in three diiferent ways: by dipping thepapers into the solution; by brushing the solution onto papers; and byspraying the papers with the solution. The products in general weresimilar having dark brown images on tan fields and appeared to be quitestable.

EXAMPLE 6 0.2 gram of oxalic acid and 10 grams of barium chloride wereadded to 100 0. cs. of aqueous solution containing the diazoniumcompound of 2 grams of N-p-(aminophenyl) morpholine hydrochloride. Papersensitized by this solution and then dried was exposed to light behind apattern and the print developed in a feebly alkaline solution ofp-oxynaphthoic acid anilide containing 0.4% of formaldehyde. The imagesobtained were dark purple, but the field showed some bleeding andrunning due to the wet development of the images.

1 gram of rescorcinol in 20 c. cs. of water was 5 3 98.444. substituted2 grams or N-(2-aminophenyl) mor-' Exam: 7 v 2.7 grams orN-p-(aminophenyl) morpholine hydrochloride were diazotized-in- 100 0.cs. 0! solution. Paper was first bathed in this solution and then in a1% alcoholic solution. of p-naphthol and allowed to dry. After exposureof the sensitized paper behind a pattern, the image was developed bybathing the exposed paper in a 0.5% aqueous solution of triethanolamine.The dried print had a red brown image on a reddish tan field, but thecontrast was somewhat interior to that obtained by ammonia development.

ExAmI8 2.0 grams of N-(3.-methyl-4-aminophenyl piperidine sulfate werediazotized in 100 c. cs. oi solution. Samples oi clear, lightweightpaper were first coated with this solution and then with a 1% alcoholicsolution of phloroglucinol and allowed to dry. Exposure and processingwere carried out as in Example 1. A brown black image on a white fieldwas developed almost immediately.

Exam 9 0.2 gram of oxalic acid and 10 grams of barium chloride in 20 0.es. of water and 0.4 gram of phloroglucinol in 4 c. es. of alcohol weresuccessively admixed with c. es. of aqueous solution containing thediazonium salt of 2.15 grams oi. N-p-(aminophenyl) morpholinehydrochloride. A piece of white, light weight paper was sensitized withthis solution, dried and exposed as.in Example 1.

The-image wasdeveloped in one case with gaseous ammonia, and in anothercase with a 0.2% aqueous sodium hydroxide solution containing inaddition 0.4% formaldehyde.

ExAMrLr: 10

The zinc chloride double salt of the diazonium 1" EXAMPLE 11 The zincchloride double salt oi! the diazonium compound of 2.15 grams oi.N-p-(aminophenyl) morpholine hydrochloride was dissolved in c. cs. ofwater. 2.0 grams of concentrated hydrochloric acid, 2.0 grams of boricacid, 4.0 grams of tartaric acid and 0.2 gram of thiourea were added tothis solution. Suitable papers were bathed in the above solution andthen in B- naphthol. The sensitized and dried papers were then exposedand developed in the manner described in Example 1. The images obtainedwere dark red on a white field and showed good keeping qualities.Samples oi paper prepared with the omission of hydrochloric, boric, andtartaric acids and of thiourea produced darker red images on very palegray fields.

While the invention has been illustrated more particularly in connectionwith azo color images formed from various N-p-aminophenyl-morpholinesand piperidines with coupling components such as p-naphthol, resorcinol,phloroglu-- cinol, 2,4-dichloro-1-naphthol, or p-oxynaphthoic sensitizedwith a number 01' u-naphthol derivaacid anilide,1t will be understoodthat other coutives and N-p-aminophenyl piperidine. These plingcomponents are likewise included within the examples were prepared ingeneral by one of the scope of the invention. For example, Table Iprocesses previously described, but contain no shows examples of printsobtained with papers 5 stabilizing substances.

TABLE I Coupling compound Preparation of coupling compound gfigggghg4-benzoyl-l-nnnh hnl Dark brown.

Moro-l-nnphfhnl 4-chloro-1-nsphthol Very dark brown. 2,4-dibromo-5-(N-benzyl-N-naphthalene-fi-sulfon) amido-l-naphthoL-Procedures I-l-IIA Brown.

-SO Ha-CoHs 16 2, 4-dichloro-E-(N-benzyl-N-a-naphthoyl) amino l-naphtholProcedures I+IIA Do.

l]I--C O OHr-CaHn V 17 2, 4-dichloro-5(N-benzy1-N-fl-naphthoy1)amino-l-naphthol Procedures I+IIA Dark brown. 18 5-hydroxy-l-naphthoicacid Do. 19 Methyl-l-naphthol-ssulfonare By heating1-acetoxynaphthalene-5- Do.

' sull'onyl chloride with excess of methyl alcohol. 204'suIiouenilide-1- p Do.

Table 11 illustrates the color of the image of naphthol couplingcomponents as specified. No dia'zotype prints obtained with paperssensitized stabilizing substances were added. with N-p-aminophenylmorpholine and various u- TABLE II Diazo compound ofN-p-aminophenyZ-morpholine coupled with E Z P Coupling compoundPreparation of coupling compound g g z gg g g 215-[p-(p-acetaminobenzene sulfonamido)-benzamido] l-naphthol Procedure VBrown.

NHC OC NHSO,-NH-C 0 on;

Z-acetyl--chloro-l-naphthol Dark brown. 2-ecetyl-1- ap ol Brown.4-acetyl-l-naphthol Dark brown.' 2-acetyl-l-naphthol-a-methyl-a-phenylhydrazone By refluxing together 2-acetyl-1- Brown.

naphthol and a-methyl-a-phenylhydrazine in alcoholic solution. OH: OH

I|-TNCnHs C-CHa 26 Z-acetyl-l-naphthol semi-car .0

4 mean Tsnu: II-Continued gg Coupling compound V Prcpuntionolcouplingcompound 27 4-bcnzoyl-l- Dllk brown. 28 o-(N-benzyi-Nn-smylmphthslene-aorp-suifon) omIdO-I-nIphthoL..- ProcodumI+I1A Brown,

OH C @CHH N-BO: Hz-CnHr 5- -benzyl-N-mphthalene-crsullon) omido-l-nshthol -.do Do. 6- N-benzyl-N-p-tert. amyl-benzeno-sulion smio-l-nsphtholdo Dc. 5- N-bcnzyl-N-n-vaieryl) amido-l-mphtho dn Do.

N-OO-CrHo Hr-CIHI 2-hromoacetyl- -na phthol Dark brown.

z-chlorc Do.

{-chloro-l-nnnhfhnl D0. #cinmmoyl-l-naphthol Brown.2,4-dibromo-5-(N-benzyl-N-ns hthaicno-fisulfon) ami Procedures I+IIA+IIIDo. 2,4-dich1oro-5-I (g-bcnzamido -benum1do]-l-naphthol--.. ProceduresV+VI Do. 2,4-dichioro-6- enzyl-N-a-nsphthoyl) smino-i-naphthoL.Procedures I+IIA+III.. Do. 2,4-dichloro-5- N-benzyl-N-fi-naphthogl)umino-l-naphthoi. 0 D 2,4-dichloro-5-palmityl-amino-l-napht o1Procedures IIA-l-III--. Do. b-fimm-dinitrobenzoylamin Ml Procedures IIBDc.

D -piperidinomethyi-1,fi-dihydroxynaphthaiene B treating 1,5-dihydroxymDu'k brown.

' one with formalin and piperidine.l-hydroxy-z-(N-isoamyl-N-phenyD-nsphthamida Procedure IV Polo brown.

co-i iw-ciml CIHI i g l-hydroxy-z-N-cthyi-N-a-nsphthyb-mphthsmideProooduroIV Brown. l-hydroxy-Z- N-methyD-naphthanilido do Do.

(IJH: 00-N-0lHl 'i"iocod""h 3'iiii.' I

By hoot l-acctoxyns hthulene- Do.

o-sulrony chloride w th excess methyl sicohol. 62 5-methy1 lulfonlamino-l-naphthol cII r Psie brown. 53 l-naphthoi-B,(sulfon-N-mcthylanilida) By condensing 1naphth0i-3,6-di- Brown.

I sulionic sold with lodium scotatc OH and scetic anhydridc, treatingthe 7 product with P01; and the istter product with mcthyisnilinc andlodium ocetatc, llld then hy- (3H1 (3H1 draining with NsOH.

CiHr-NSO Oz-N-Cfls i' fiifighcuu fx iil hthdido) B co d in4- r i i hkbbmwn' on y nens po on owns e rown; p thslene lullonyl chori& withaethyinaphthyhmino and sodium izoetsto Ind hydrolyzing with s 5-nitrobcnumido)-l-mphthol Procoduro IIB.. Brown.o-ggsuifamylbenzamidoyl-mphthoi Procedure 11A. Dsrk brown.I-nwnleryi-l-mphthol... By hating mmph oiwi Bro 4- n1 11 hthai n fl i ii i x n' l n D n- -na 1 arms 0 o. w w p thliene with vuleryl chloride31d duminum chloride.

In the above tables, reference has been made to the procedures forpreparing some of the coupling compounds disclosed. These generalprocedures are briefly described in the following:

I. -benzylamino-1-naphthol was prepared by condensing5-amino-1-naphthol. with benzaldehyde and reducing the resultant Schiflbase catalytically or chemically.

lI(A) 5-acylamino-l-naphthols were prepared by condensing 2 moles of5-amino-l-naphthol or 2 moles of a 5-alky1amino-1-naphthol with 1 moleof XCl, wherein X represents an acyl group.

(B). By condensing -1 mole of the naphthol compound with 1 mole of XClin the presence of sodium acetate and acetic acid.

III. Halogenated 5-acylamino-l-naphthols of procedure II were preparedby treatment with sulfuryl chloride or bromine in a suitable solvent.

IV. l-hydroxy-2-naphthamides were prepared by condensing 1 mole ofl-hydroxy-2-naphthoyl chloride with 2 moles of a compound having theformula RNHR' wherein R and R may be hydrogen, alkyl or aryl.

Y. 5 (p acylaminobenzamido) -1 naphthols were prepared by condensing a5-amino-l-naphthol with p-nitrobenzoyl' chloride. reducing the nitrogroup and then reacting with sodium acetate and X01, wherein Xrepresents an acyl group.

VI. Halogenated 5-(p-acylaminobenzamido) -1- naphthols were prepared bytreatment with sulfuryl chloride or bromine in a suitable solvent.

Although the examples of Tables I and II refer particularly to couplingwith the diazo derivatives of N-p-aminophenyl piperidine andN-paminophenyl morpholine, respectively, it will be apparent from allthe foregoing that similar results can be obtained with the variousmethyl, halogen, methoxy and sulphonic acid substituted diazoderivatives of these compounds.

we claim:

1. A light sensitive diazotype material comprising a light sensitivediazo derivative of a compound the general formula:

wherein R represents a benzene nucleus, and Z represents thenon-metallic elements necessary to complete a morpholine nucleus.

2. A light sensitive diazotype material comprising a light sensitivediazo derivative of a compound having the general formula:

wherein R represents a benzene nucleus.

3. A light sensitive diazotype material comprising a light sensitivediazo derivative of a compound having the general formula:

/C Hr-C H. O

CHrC:

wherein R represents a benzene nucleus, and Z represents thenon-metallic elements necessary to complete a morpholine nucleus, and acoupling component selected from the group consisting of a phenolcompound, and a naphthol compound.

ARNOLD WEISSBERGER.

WALDEMAR VANSELOW.

